EP0906411B1 - Compositions de cristaux liquides - Google Patents

Compositions de cristaux liquides Download PDF

Info

Publication number
EP0906411B1
EP0906411B1 EP97929890A EP97929890A EP0906411B1 EP 0906411 B1 EP0906411 B1 EP 0906411B1 EP 97929890 A EP97929890 A EP 97929890A EP 97929890 A EP97929890 A EP 97929890A EP 0906411 B1 EP0906411 B1 EP 0906411B1
Authority
EP
European Patent Office
Prior art keywords
glycol
composition
liquid crystal
soil
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97929890A
Other languages
German (de)
English (en)
Other versions
EP0906411A1 (fr
Inventor
Jean Massaux
Georges Yianakopoulos
Genevieve Blandiaux
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP0906411A1 publication Critical patent/EP0906411A1/fr
Application granted granted Critical
Publication of EP0906411B1 publication Critical patent/EP0906411B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to an anticream detergent composition containing an abrasive. More specifically, it is of a liquid detergent composition in liquid crystal state which when brought into contact with oily soil is superior to other liquid detergent compositions in detergency and in other physical properties.
  • Liquid aqueous synthetic organic detergent compositions have long been employed for human hair shampoos and as dishwashing detergents for hand washing of dishes (as distinguished from automatic dishwashing machine washing of dishes). Liquid detergent compositions have also been employed as hard surface cleaners, as in pine oil liquids, for cleaning floors and walls. More recently they have proven successful as laundry detergents too, apparently because they are convenient to use, are instantly soluble in wash water, and may be employed in "pre-spotting" applications to facilitate removals of soils and stains from laundry upon subsequent washing. Liquid detergent compositions have comprised anionic, cationic and nonionic surface active agents, builders and adjuvants, including, as adjuvants, lipophilic materials which can act as solvents for lipophilic soils and stains. The various liquid aqueous synthetic organic detergent compositions mentioned serve to emulsify lipophilic materials, including oily soils, in aqueous media, such as wash water, by forming micellar dispersions and emulsions.
  • microemulsions Although emulsification is a mechanism of soil removal, it has been only comparatively recently that it was discovered how to make microemulsions which are much more effective than ordinary emulsions in removing lipophilic materials from substrates.
  • microemulsions are described in British Patent Specification No. 2,190,681 and in U.S. Patents 5,075,026; 5,076,954 and 5,082,584 and 5,108,643, most of which relate to acidic microemulsions useful for cleaning hard surfaced items, such as bathtubs and sinks which microemulsions are especially effective in removing soap scum and time scale from them.
  • microemulsions may be essentially neutral and such are also taught to be effective for microemulsifying lipophilic soils from substrates.
  • U.S. Patent No. 5,415,812 there is described a light duty microemulsion liquid detergent composition which is useful for washing dishes and removing greasy deposits from them in both neat and diluted forms.
  • Such compositions include complexes of anionic and cationic detergents as surface active components of the microemulsions.
  • the various microemulsions referred to include a lipophile, which may be a hydrocarbon, a surfactant, which may be an anionic and/or a nonionic detergent(s), a co-surfactant, which may be a poly-lower alkylene glycol lower alkyl ether, e.g., tripropylene glycol monomethyl ether, and water.
  • a lipophile which may be a hydrocarbon
  • a surfactant which may be an anionic and/or a nonionic detergent(s)
  • a co-surfactant which may be a poly-lower alkylene glycol lower alkyl ether, e.g., tripropylene glycol monomethyl ether, and water.
  • the present invention improves them still further and also increases the capacity of the detergent compositions to adhere to surfaces to which they have been applied. Thus, they drop or run substantially less than cleaning compositions of "similar" cleaning power which are in microemulsion or normal liquid detergent form. Also, because they form microemulsions with lipophilic soil or stain material spontaneously, with essentially no requirement for addition of any energy, either thermal or mechanical, they are more effective cleaners at room temperature and at higher and lower temperatures that are normally employed in cleaning operations than are ordinary liquid detergents, and are also more effective than detergent compositions in microemulsion form.
  • the present liquid crystal detergent compositions may be either clear or somewhat cloudy or milky (opalescent) in appearance but both forms thereof are stable on storage and components thereof do not settle out or become ineffective, even on storage at somewhat elevated temperatures for periods as long as six months and up to a year.
  • the presence of the cosurfactant in the liquid crystal detergent compositions helps to make such compositions resist freezing at low temperatures.
  • a liquid detergent composition containing an abrasive, suitable at room temperature or colder, for pre-treating and cleaning materials soiled with lipophilic soil is in liquid crystal form and comprises synthetic organic surface active agents, a cosurfactant, a solvent for the soil, and water.
  • the invention also relates to processes for treating items and materials soiled with lipophilic soil with compositions of this invention to loosen or remove such soil, by applying to the locus of such soil on such material a soil loosening or removing amount of an invented composition.
  • lipophilic soil is absorbed from the soiled surface into the liquid crystal.
  • all-purpose liquid detergents have become widely accepted for cleaning hard surfaces, e.g., painted woodwork and panels, tiled walls, wash bowls, bathtubs, linoleum or tile floors, washable wall paper, etc.
  • Such all-purpose liquids comprise clear and opaque aqueous mixtures of water-soluble synthetic organic detergents and water-soluble detergent builder salts.
  • use of water-soluble inorganic phosphate builder salts was favored in the prior art all-purpose liquids.
  • such early phosphate-containing compositions are described in U.S. Patent Nos. 2,560,839; 3,234,138; 3,350,319; and British Patent No. 1,223,739.
  • U.S. Patent No. 4,017,409 teaches that a mixture of paraffin sulfonate and a reduced concentration of inorganic phosphate builder salt should be employed.
  • such compositions are not completely acceptable from an environmental point of view based upon the phosphate content.
  • another alternative to achieving phosphate-free all-purpose liquids has been to use a major proportion of a mixture of anionic and nonionic detergents with minor amounts of glycol ether solvent and organic amine as shown in U.S. Patent NO. 3,935,130. Again, this approach has not been completely satisfactory and the high levels of organic detergents necessary to achieve cleaning cause foaming which, in turn, leads to the need for thorough rinsing which has been found to be undesirable to today's consumers.
  • an o/w microemulsion is a spontaneously forming colloidal dispersion of "oil” phase particles having a particle size in the range of 25 to 800 ⁇ in a continuous aqueous phase.
  • microemulsions are transparent to light and are clear and usually highly stable against phase separation.
  • Patent disclosures relating to use of grease-removal solvents in o/w microemulsions include, for example, European Patent Applications EP 0137615 and EP 0137616 - Herbots et al; European Patent Application EP 0160762 - Johnston et al; and U.S. Patent No. 4,561,991- Herbots et al. Each of these patent disclosures also teaches using at least 5% by weight of grease-removal solvent.
  • compositions of this invention described by Herbots et al. require at least 5% of the mixture of grease-removal solvent and magnesium salt and preferably at least 5% of solvent (which may be a mixture of water-immiscible non-polar solvent with a sparingly soluble slightly polar solvent) and at least 0.1% magnesium salt.
  • Liquid detergent compositions which include terpenes, such as d-limonene, or other grease-removal solvent, although not disclosed to be in the form of o/w microemulsions, are the subject matter of the following representative patent documents: European Patent Application 0080749; British Patent Specification 1,603,047; and U.S. Patent Nos. 4,414,128 and 4,540,505.
  • U.S. Patent No. 4,414,128 broadly discloses an aqueous liquid detergent composition characterized by, by weight:
  • EP-A 0 335 471 discloses compositions having a liquid crystal structure further comprising an abrasive and as an essential part of this composition a builder salt.
  • the present invention relates to improved, liquid crystal detergent compositions containing an abrasive.
  • the compositions have improved scouring ability and interfacial tension which improves the cleaning of hard surface such as plastic, vitreous and metal surfaces having a shiny finish, oil stained floors, automotive engines and other engines.
  • the improved cleaning compositions exhibit good scouring power and grease soil removal properties due to the improved interfacial tensions and leave the cleaned surfaces shiny without the need of or requiring only minimal additional rinsing or wiping.
  • the latter characteristic is evidenced by little or no visible residues on the unrinsed cleaned surfaces and, accordingly, overcomes one of the disadvantages of prior art products.
  • the invention generally provides a stable, liquid crystal, hard surface cleaning composition especially effective in the removal of oily and greasy oil.
  • the liquid crystal composition includes, on a weight basis:
  • the present invention relates to a liquid crystal detergent composition which comprises by weight:
  • the role of the water insoluble hydrocarbon can be provided by a non-watersoluble perfume.
  • a solublizer such as alkali metal lower alkyl aryl sulfonate hydrotrope, triethanolamine, urea, etc.
  • perfume dissolution especially at perfume levels of 1% and higher, since perfumes are generally a mixture of fragrant essential oils and aromatic compounds which are generally not water-soluble.
  • perfume is used in its ordinary sense to refer to and include any non-water soluble fragrant substance or mixture of substances including natural (i.e., obtained by extraction of flower, herb, blossom or plant), artificial (i.e., mixture of natural oils or oil constituents) and synthetically produced substance) odoriferous substances.
  • perfumes are complex mixtures of blends of various organic compounds such as alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils (e.g., terpenes) such as from 0% to 80%, usually from 10% to 70% by weight, the essential oils themselves being volatile odoriferous compounds and also serving to dissolve the other components of the perfume.
  • the perfume is not, per se, a solvent for greasy or oily soil, --even though some perfumes may, in fact, contain as much as 80% of terpenes which are known as good grease solvents -- the inventive compositions in dilute form have the capacity to solubilize up to 10 times or more of the weight of the perfume of oily and greasy soil, which is removed or loosened from the hard surface by virtue of the action of the anionic and nonionic surfactants, said soil being taken up into the oil phase of the o/w microemulsion.
  • the precise composition of the perfume is of no particular consequence to cleaning performance so long as it meets the criteria of water immiscibility and having a pleasing odor.
  • the perfume, as well as all other ingredients should be cosmetically acceptable, i.e., non-toxic, hypoallergenic, etc.
  • the hydrocarbon such as a perfume is present in the liquid crystal composition in an amount of from 0.02% to 6% by weight, preferably from 0.05% to 6% by weight. If the hydrocarbon (perfume) is added in amounts more than 6% by weight, the cost is increased without any additional cleaning benefit and, in fact, with some diminishing of cleaning performance insofar as the total amount of greasy or oily soil which can be taken up in the oil phase of the microemulsion will decrease proportionately.
  • the liquid crystal cleaning compositions of the present invention may often include as much as 0.2% to 7% by weight, based on the total composition, of terpene solvents introduced thereinto via the perfume component.
  • the amount of terpene solvent in the cleaning formulation is less than 1.5% by weight, such as up to 0.6% by weight or 0.4% by weight or less, satisfactory grease removal and oil removal capacity is provided by the inventive compositions.
  • Suitable essential oils are selected from the group consisting of: Anethole 20/21 natural, Aniseed oil china star, Aniseed oil globe brand, Balsam (Peru), Basil oil (India), Black pepper oil, Black pepper oleoresin 40/20, Bois de Rose (Brazil) FOB, Borneol Flakes (China), Camphor oil, White, Camphor powder synthetic technical, Cananga oil (Java), Cardamom oil, Cassia oil (China), Cedarwood oil (China) BP, Cinnamon bark oil, Cinnamon leaf oil, Citronella oil, Clove bud oil, Clove leaf, Coriander (Russia), Coumarin 69°C (China), Cyclamen Aldehyde, Diphenyl oxide, Ethyl vanilin, Eucalyptol, Eucalyptus oil, Eucalyptus citriodora, Fennel oil, Geranium oil, Ginger oil, Ginger oleoresin (India), White grapefruit oil, Guaiacwood oil, Gurjun bals
  • the at least one nonionic surfactant is present in amounts of about 1% to 20%, preferably 2% to 8% by weight of the liquid crystal composition and provides superior performance in the removal of oily soil and mildness to human skin.
  • the water soluble ethoxylated nonionic surfactants utilized in this invention are commercially well known and include the primary aliphatic alcohol ethoxylates and secondary aliphatic alcohol ethoxylates.
  • the length of the polyethenoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
  • the nonionic surfactant class includes the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 16 carbon atoms in a straight or branched chain configuration) condensed with about 2 to 20 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide (EO), tridecanol condensed with about 6 to moles of EO, myristyl alcohol condensed with about 10 moles of EO per mole of myristyl alcohol, the condensation product of EO with a cut of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of EO per mole of total alcohol or about 9 moles of EO per mole of alcohol and tallow alcohol ethoxylates containing 6 EO to 11 EO per mole of alcohol.
  • a higher alcohol e.g.
  • NeodolTM ethoxylates which are higher aliphatic, primary alcohol containing about 9-15 carbon atoms, such as C 9 -C 11 alkanol condensed with 2 to 10 moles of ethylene oxide (Neodol 91-8, Neodol 91-5 or Neodol 91-2.5), C 12-13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C 12-15 alkanol condensed with 12 moles ethylene oxide (Neodol 25-12), C 14-15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like.
  • NeodolTM ethoxylates such as C 9 -C 11 alkanol condensed with 2 to 10 moles of ethylene oxide (Neodol 91-8, Neodol 91-5 or Neodol 91-2.5), C 12-13 alkanol condensed with 6.5 moles ethylene
  • Such ethoxamers have an HLB (hydrophobic lipophilic balance) value of about 8 to 15 and give good O/W emulsification, whereas ethoxamers with HLB values below 7 contain less than 4 ethyleneoxide groups and tend to be poor emulsifiers and poor detergents.
  • HLB hydrophobic lipophilic balance
  • Additional satisfactory water soluble alcohol ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration condensed with 5 to 30 moles of ethylene oxide.
  • Examples of commercially available nonionic detergents of the foregoing type are C 11 -C 15 secondary alkanol condensed with either 9 EO (TergitolTM 15-S-9) or 12 EO (Targitol 15-S-12) marketed by Union Carbide.
  • B is selected from the group consisting of hydrogen or a group represented by: wherein R is selected from the group consisting of alkyl group having 6 to 22 carbon atoms, more preferably about 12 to about 16 carbon atoms and alkenyl groups having about 6 to 22 carbon atoms, more preferably about 12 to 16 carbon atoms, wherein a hydrogenated tallow alkyl chain or a coco alkyl chain is most preferred, wherein at least one of the B groups is represented by said R' is selected from the group consisting of hydrogen and methyl groups; x, y and z have a value between 0 and 60, more preferably 0 to 40, provided that (x+y+z) equals about 2 to about 100, preferably 4 to about 24 and most preferably about 6 to 19, wherein in Formula (I) the ratio of mono
  • the esterified polyethoxyether surfactant (ethoxylated glycerol esters) used in the instant composition is manufactured by the Kao Corporation and sold under the trade name Levenol such as Levenol F-200 which has an average EO of 6 and a molar ratio between glycerol and coco fatty acid of 0.55 or Levenol V501/2 which has an average EO of 17 and a molar ratio between glycerol and coco fatty acid of 1.5.
  • the esterified polyethoxyether surfactant has a molecular weight of about 400 to about 1600, and a pH (50 grams / liter of water) of 5-7.
  • the Levenol nonionic detergents are substantially non irritant to human skin and have a primary biodegradabillity higher than 90% as measured by the Wickbold method Bias-7d.
  • Levenol V-501/2 which has 17 ethoxylated groups and is derived from tallow fatty acid with a fatty acid to glycerol ratio of 1.5 and a molecular weight of 1465
  • Levenol F-200 has 6 ethoxylated groups and is derived from coco fatty acid with a fatty acid to glycerol ratio of 0.55.
  • the Levenol (esterified polyethoxyether nonionic detergent) has ecoxicity values of algae growth inhibition > 100 mg/liter; acute toxicity for Daphniae > 100 mg/liter and acute fish toxicity > 100 mg/liter.
  • the Levenol has a ready biodegradability higher than 60% which is the minimum required value according to OEOD 301B measurement to be acceptably biodegradable.
  • polyesterified nonionic surfactants useful in the instant compositions are CrovolTM PK-4C and CrovolTM PK-70 manufactured by Croda GMBH of the Netherlands.
  • CrovolTM PK-40 is a polyoxyethylene (12) Palm Kernel Glyceride which has 12 EO groups.
  • CrovolTM PK-70 which is preferred is a polyoxyethylene (45) Palm Kernel Glyceride have 45 EO groups.
  • the anionic surfactant which is used in the instant compositions at a concentration of about 1wt. % to about 30 wt. %, more preferably about 4 wt. % to about 20 wt. % is a magnesium salt of a C 8 -C 16 linear alkyl benzene sulfonate surfactant.
  • the major class of compounds found to provide cosurfactants for the liquid crystal over temperature ranges extending from 5°C to 43°C for instance are glycerol, ethylene glycol, water-soluble polyethylene glycols having a molecular weight of 300 to 1000, polypropylene glycol of the formula HO(CH 3 CHCH 2 O) n H wherein n is a number from 2 to 18, mixtures of polyethylene glycol and polypropyl glycol (SynaloxTM) and mono C 1 -C 6 alkyl ethers and esters of ethylene glycol and propylene glycol having the structural formulas R(X) n OH and R 1 (X) n OH wherein R is C 1 -C 6 alkyl group, R 1 is C 2 -C 4 acyl group, X is (OCH 2 CH 2 ) or (OCH 2 (CH 3 )CH) and n is a number from 1 to 4, diethylene glycol, triethylene glycol, an alkyl lactate, wherein the
  • Representative members of the polypropylene glycol include dipropylene glycol and polypropylene glycol having a molecular weight of 200 to 1000, e.g., polypropylene glycol 400.
  • Other satisfactory glycol ethers are ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monobutyl ether, mono, di, tri propylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, mono, di, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, propylene glycol tertiary butyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol monopentyl ether, diethylene glycol mono
  • the amount of cosurfactant required to stabilize the liquid crystal compositions will, of course, depend on such factors as the surface tension characteristics of the cosurfactant, the type and amounts of the primary surfactants and perfumes, and the type and amounts of any other additional ingredients which may be present in the composition and which have an influence on the thermodynamic factors enumerated above.
  • the amounts of cosurfactant used in the liquid crystal composition is in the range of from 1% to 20%, preferably from 2% to 15%, by weight provide stable dilute liquid crystal composition for the above-described levels of primary surfactants and perfume and any other additional ingredients as described below.
  • the instant liquid crystal compositions contain about 0.1 to 10 wt. %, more preferably 0.25 to 6 wt. % of an abrasive selected from the group consisting of calcite, amorphous hydrated silica and polyethylene powder particles.
  • the amorphous silica (oral grade) used to enhanca the scouring ability of the liquid crystal gel was provided ZeoffinTM (Zeoffin 115)
  • ZeoffinTM 115 The mean particles size of ZeoffinTM 115 is about 8to about 15 ⁇ m. Its apparent density is about 0.32 to about 0.37 g/ml.
  • Another amorphous silica from Rhone-Poulenc is TixosilTM 103 having a mean particle size of 8 to 12 ⁇ m and an apparent density of 0.25-0.4 g/ml.
  • Another abrasive which can be used is a polyethylene powder having a particle size of about 200 to about 500 microns and a density of about 0.91 to about 0.99 g/liter, more preferably about 0.94 to about 0.96.
  • calcite used at a concentration of about 0 to 20 wt. %, more preferably 1 wt. % to 10 wt. % such as the calcite manufactured by J. M. Huber Corporation of Illinois.
  • Calcite is a limestone consisting primarily of calcium carbonate and 1% to 5% of magnesium carbonate which has a mean particle size of 5 microns and oil absorption (rubout) of about 10 and a hardness of about 3.0 Mohs.
  • liquid crystal formulations In addition to their excellent scouring ability and capacity for cleaning greasy and oily soils, the nearly neutral pH (pH from about 4.5 to about 5) liquid crystal formulations also exhibit excellent cleaning performance and removal of soap scum and lime scale in neat (undiluted) as well as in diluted usage.
  • the instant composition contains about 0 to about 10 wt. %, more preferably about 0.2 to about 8 wt. % of a magnesium salt such as magnesium chloride and/or magnesium sulfate heptahydrate and mixtures thereof, and more preferably Magnesium oxide (MgO).
  • Mg(LAS)2 is first of all formed by reaction between MgO and LAS sulfonic acid. Then the other active ingredients are added to form liquid crystal structure.
  • the final essential ingredient in the inventive liquid crystal compositions having improved interfacial tension properties is water.
  • the proportion of waler in the liquid crystal detergent composition generally is in the range of 20% to 97%, preferably 70% to 97% by weight.
  • a composition of this invention is in a liquid crystal state when it is of lypotropic structure, is transparent or slightly turbid (opalescent) but no opaque, and has a storage modulus equal to or higher than one Pascal (1 Newton/sq, m.), more preferably higher than 10 Pascal and most preferably higher than 20 Pascal and when measured at a temperature of 4 to 50°C, at a frequency of 1 radian per second and at a strain of 0.1 to 5%.
  • the rheological behavior of the compositions of this invention were measured at 25°C by means of a Carri-Med CS Rheometer. In making the measurement.
  • a cone and plate are used at a cone angle of 2 degrees: 0 minutes: 0 seconds with a cone diameter of 4.0 cm, measurement system gap of 53.0 micro m and a measurement system inertia of 4.35 micro Nm sec -2 .
  • liquid crystal compositions of the invention is relatively simple because they tend to form spontaneously with little need for the addition of energy to promote transformation to the liquid crystal state.
  • mixing will normally be undertaken and it has been found desirable first to mix the surfactants and cosurfactant into water and then followed by admixing of the lipophilic component, usually a hydrocarbon (but esters or mixtures of hydrocarbons and esters may also be employed). It is not necessary to employ heat and most mixings are preferably carried out at about room temperature (20-25°C).
  • compositions may be applied to such surfaces by pouring onto them, by application with a cloth or sponge, or by various other contacting means but it is preferred to apply them in the form of a spray by spraying them onto the substrate from a hand or finger pressure operated sprayer or squeeze bottle.
  • Such application may be onto hard surfaces, such as dishes, walls or floors, from which lipophilic (usually greasy or oily) soil is to be removed, or may be onto fabrics, such as laundry, which has previously been stained with lipophilic soils, such as motor oil.
  • the invented compositions may be used as detergents and as such may be employed in the same manner in which liquid detergents are normally utilized in dishwashing, floor and wall cleaning and laundering, but it is preferred that they be employed as pre-spotting agents too, in which applications they are found to be extremely useful in loosening the adhesions of lipophilic soils to substrates, thereby promoting much easier cleaning with application of more of the same invented detergent compositions or by applications of different commercial detergent compositions, in liquid, bar or particulate forms.
  • the invention relates to the important discovery that effective liquid detergent compositions can be made in the liquid crystal state and that because they are in such state they are especially effective in removing lipophilic soils from substrates and also are effective in removing from substrates non-lipophilic materials.
  • Such desirable properties of the liquid crystal detergent compositions of this invention make them ideal for use as pre-spotting agents and detergents for removing hard-to-remove soils from substrates in various hard and soft surface cleaning operations.
  • strokes number proto strokes number ref., then the index is 0 (cleaning equivalence between prototype and reference).
  • strokes number proto strokes number ref. then the index is characterized by a negative value (the more negative the index, the less efficient the prototype).
  • the index is characterized by a positive value (the more positive the index, the more efficient the prototype).
  • the thermal stability of the samples were measured by _classic ageing test (put 100ml of product for several weeks at 4oC, R.T, 35oC and 43oC). We also can predict the thermal stability by rheological measurements (G' and G"as a function of Temperature).The more stable G' values all over the Temperature range 4-43°C, the more stable the prototype.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Liquid Crystal Substances (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Cosmetics (AREA)

Claims (5)

  1. Composition détergente sous forme de cristaux liquides comprenant en poids :
    (a) 1 à 20% d'au moins un tensioactif non ionique contenant des groupements éthylène oxyde ;
    (b) 1 à 30% d'un sel de magnésium d'un tensioactif du type alkylbenzène sulfonate en C8-C16 ;
    (c) 0,1 % à 10% en poids d'un abrasif choisi parmi le groupe consistant en calcite, poudre de polyéthylène et silice amorphe ;
    (d) 1% à 20% d'un co-surfactant choisi parmi le groupe des glycérol, éthylène glycol, des polyéthylènes glycol hydrosolubles possédant un poids moléculaire de 300 à 1000, de polypropylène glycol de formule HO(CH3CHCH2O)nH dans laquelle n est un entier de 2 à 18, les mélanges de polyéthylène glycol et polypropylglycol et mono alkyléthers en C1-C6 et esters d'éthylène glycol et propylène glycol possédant des formules structurelles R(X)nOH et R1(X)nOH dans lesquelles R est un groupement alkyle en C1-C6, R1 est un groupement acyle en C2-C4, X est (OCH2CH2) ou (OCH2(CH3)CH) et n est un entier de 1 à 4, diéthylène glycol, triéthylène glycol, et lactate d'alkyle dans lequel le groupe alkyle possède 1 à 6 atomes de carbone, 1-méthoxy-2-propanol, 1-méthoxy-3-propanol, et 1-méthoxy 2-, 3- ou 4-butanol;
    (e) 0,02% à 6% d'un composé organique non hydrosoluble choisi parmi le groupe consistant en parfums, huiles essentielles et hydrocarbures non hydrosolubles possédant 8 à 18 atomes de carbone ; et
    (f) 0,1% à 3% d'un acide gras insaturé possédant 12 à 20 atomes de carbone ; et
    (g) la balance étant de l'eau,
       avec ladite composition ne contenant aucun tensioactif sulfaté, caractérisée en ce que la composition sous forme de cristaux liquides possède un module d'accumulation d'au moins 1 N/m2 mesurée à une température comprise entre 4 et 50°C à une contrainte de 0,1% à 5% et une fréquence de 1 radian/seconde sur un rhéomètre Carri-Med CS et est thermiquement stable et monophasique à une température de 8-43°C.
  2. Composition selon la revendication 1, dans laquelle ledit tensioactif non ionique est un produit de condensation d'un alcool d'acide gras élevé possédant 9 à 11 atomes de carbone avec 2 à 6 moles dudit groupement d'oxyde d'éthylène.
  3. Composition selon la revendication 2, dans laquelle ledit co-surfactant est l'éther n-butylique de tripropylène glycol.
  4. Procédé pour traiter les matériaux souillés par des salissures lipophiles à éliminer ou détacher qui comprend l'application sur la zone souillée du matériau d'une quantité efficace pour éliminer ou détacher de la composition selon la revendication 1.
  5. Procédé selon la revendication 4, caractérisé en ce que la composition est appliquée à titre de pré-traitement au niveau du matériau souillé avec des salissures lipophiles difficiles à éliminer, sur la zone concernée dudit matériau, de manière à ce que la tache soit ensuite éliminée par application d'une composition détergente identique ou diffiérente et de l'eau.
EP97929890A 1996-06-14 1997-06-11 Compositions de cristaux liquides Expired - Lifetime EP0906411B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US66437096A 1996-06-14 1996-06-14
US664370 1996-06-14
PCT/US1997/010015 WO1997047726A1 (fr) 1996-06-14 1997-06-11 Compositions de cristaux liquides

Publications (2)

Publication Number Publication Date
EP0906411A1 EP0906411A1 (fr) 1999-04-07
EP0906411B1 true EP0906411B1 (fr) 2001-11-21

Family

ID=24665724

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97929890A Expired - Lifetime EP0906411B1 (fr) 1996-06-14 1997-06-11 Compositions de cristaux liquides

Country Status (13)

Country Link
US (1) US5849105A (fr)
EP (1) EP0906411B1 (fr)
AR (1) AR009946A1 (fr)
AT (1) ATE209249T1 (fr)
AU (1) AU713425B2 (fr)
BG (1) BG63605B1 (fr)
CO (1) CO4870723A1 (fr)
DE (1) DE69709733D1 (fr)
HU (1) HUP9903434A3 (fr)
MY (1) MY122086A (fr)
NZ (1) NZ333153A (fr)
PL (1) PL186884B1 (fr)
WO (1) WO1997047726A1 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19935083A1 (de) * 1999-07-29 2001-02-08 Benckiser Nv Reinigungsmittel für glaskeramische Oberflächen
US6159925A (en) * 2000-04-06 2000-12-12 Colgate-Palmolive Co. Acidic liquid crystal compositions
US20030125226A1 (en) * 2000-11-28 2003-07-03 Lewis Paul F. Anti-slip floor coating remover composition
US6337312B1 (en) * 2001-05-11 2002-01-08 Colgate-Palmolive Co Liquid crystal compositions comprising an abrasive and magnesium sulfate heptahydrate
US6737394B2 (en) * 2002-03-04 2004-05-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Isotropic cleansing composition with benefit agent particles
US6797683B2 (en) * 2002-03-04 2004-09-28 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Ordered liquid crystalline cleansing composition with benefit agent particles
DE10344938A1 (de) * 2003-09-27 2005-04-21 Clariant Gmbh Tensid-Compounds enthaltend Fettalkoholalkoxylate
EP1874910B1 (fr) * 2005-04-14 2014-04-30 Koninklijke Philips N.V. Liquide nettoyant pour appareil electrique de soins personnels
BR112017004466A2 (pt) * 2014-09-11 2017-12-05 Unilever Nv composição em creme para limpeza de superfícies rígidas, uso de uma composição em creme e método de remoção de depósitos de manchas de óleo ou gordura incrustadas de uma superfície rígida
BR112017004467A2 (pt) * 2014-09-11 2017-12-05 Unilever Nv composição em creme para limpeza de superfícies rígidas, método de remoção de depósitos de manchas de óleo ou gordura incrustadas de uma superfície rígida, processo de preparação e uso da mesma
BR112018004605B1 (pt) * 2015-09-15 2022-06-07 Unilever Ip Holdings B.V. Composição aquosa abrasiva de limpeza
WO2018091226A1 (fr) * 2016-11-18 2018-05-24 Unilever N.V. Composition aqueuse pour le nettoyage de surfaces dures

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1534680A (en) * 1977-10-14 1978-12-06 Colgate Palmolive Co Cleaning compositions
US4414128A (en) * 1981-06-08 1983-11-08 The Procter & Gamble Company Liquid detergent compositions
JPS6081298A (ja) * 1983-10-11 1985-05-09 花王株式会社 研摩剤含有液状洗浄剤組成物
GB8409054D0 (en) * 1984-04-07 1984-05-16 Procter & Gamble Stabilized oil-in-water cleaning microemulsions
US5076954A (en) * 1986-05-21 1991-12-31 Colgate-Palmolive Company Stable microemulsion cleaning composition
US4804491A (en) * 1986-11-03 1989-02-14 The Clorox Company Aqueous based acidic hard surface cleaner
US4869842A (en) * 1988-03-31 1989-09-26 Colgate-Palmolive Co. Liquid abrasive cleansing composition containing grease-removal solvent
GB8823655D0 (en) * 1988-10-07 1988-11-16 Unilever Plc Liquid detergent compositions
US5035826A (en) * 1989-09-22 1991-07-30 Colgate-Palmolive Company Liquid crystal detergent composition
WO1992003528A1 (fr) * 1990-08-22 1992-03-05 R & C Products Pty. Ltd. Produits nettoyants pour surfaces dures
DE69320355T2 (de) * 1992-09-09 1999-02-11 Unilever N.V., Rotterdam Verbesserung von reinigern für harte oberflächen
SK53294A3 (en) * 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use

Also Published As

Publication number Publication date
WO1997047726A1 (fr) 1997-12-18
PL186884B1 (pl) 2004-03-31
AU3384397A (en) 1998-01-07
ATE209249T1 (de) 2001-12-15
MY122086A (en) 2006-03-31
BG63605B1 (bg) 2002-06-28
PL330641A1 (en) 1999-05-24
CO4870723A1 (es) 1999-12-27
AR009946A1 (es) 2000-05-17
US5849105A (en) 1998-12-15
EP0906411A1 (fr) 1999-04-07
DE69709733D1 (de) 2002-02-21
HUP9903434A3 (en) 2001-02-28
NZ333153A (en) 2000-07-28
AU713425B2 (en) 1999-12-02
HUP9903434A2 (hu) 2000-03-28
BG103017A (en) 1999-09-30

Similar Documents

Publication Publication Date Title
US6159925A (en) Acidic liquid crystal compositions
US5898026A (en) Liquid crystal compositions
AU2001253046A1 (en) Acidic liquid crystal detergent compositions
US5707957A (en) Liquid crystal compositions
US5958852A (en) Liquid crystal compositions containing alpha hydroxy aliphatic acid
AU711740B2 (en) Liquid crystal detergent compositions
EP0906411B1 (fr) Compositions de cristaux liquides
US5723431A (en) Liquid crystal compositions
EP0912713B1 (fr) Composition de cristaux liquides
US5703028A (en) Liquid crystal detergent compositions based on anionic sulfonate-ether sulfate mixtures
US5958856A (en) Liquid crystal compositions containing a polyethylene abrasive
US5759290A (en) Liquid crystal compositions
AU711075B2 (en) Liquid crystal detergent compositions
US5922666A (en) Liquid crystal compositions

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19981222

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI NL PT SE

AX Request for extension of the european patent

Free format text: RO PAYMENT 981222

17Q First examination report despatched

Effective date: 19991108

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LI NL PT SE

AX Request for extension of the european patent

Free format text: RO PAYMENT 19981222

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011121

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011121

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 20011121

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011121

Ref country code: FR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011121

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011121

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011121

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011121

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20011121

REF Corresponds to:

Ref document number: 209249

Country of ref document: AT

Date of ref document: 20011215

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020221

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020221

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020221

REF Corresponds to:

Ref document number: 69709733

Country of ref document: DE

Date of ref document: 20020221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020222

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020530

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020611

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020611

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

EN Fr: translation not filed
26N No opposition filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20020611

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A